TWI670756B - Fcvd line bending resolution by deposition modulation - Google Patents

Abstract

A method of reducing surface roughness and line bending of a pillared substrate includes treating the substrate containing the pillars with free radicals to form a treated surface. The free radical can be a thiol group, a nitrogen group or an oxy group. The method includes reacting an organic hafnium precursor with an oxygen precursor to form a dielectric film over the treated surface. The method includes curing the dielectric film at a temperature of about 150 ° C or below. A method of reducing surface roughness and line bending of a substrate having a pillar includes reacting an organic tantalum precursor, an oxygen precursor, and a radical precursor to form a dielectric film on the substrate including the pillar. The method includes curing the dielectric film at a temperature of about 150 ° C or below. The free radical precursor may be selected from the group consisting of a nitrogen radical precursor, an oxy radical precursor, and a sulfhydryl radical precursor.

Description

Resolve FCVD line bending by deposition adjustment

Embodiments of the invention are directed to surface treatment and formation of dielectric films.

As the device nodes shrink, the narrow, high aspect ratio struts become mechanically fragile and tend to bend due to stress or force imbalance during deposition. For example, high aspect ratio ruthenium oxide pillars are susceptible to this bending. The stress or force imbalance around the elongated struts may be caused by capillary forces and flow chemical vapor deposition (FCVD) half-moon profiles, viscous forces between FCVD deposition and the substrate (eg, caused by intermolecular forces between the dangling bonds) and / Or caused by local stress caused by surface roughness.

1 is a schematic cross-sectional view showing a portion of a semiconductor device 100 in which line bending occurs between two pillars in the semiconductor device 100. As shown in Fig. 1, the high aspect ratio device structure is formed on the surface of the substrate. During processing, the device post 102 should remain oriented in a vertical orientation and the wall 106 should not traverse the opening 104 and the abutting wall 106 of the contact post 102. The wall surface 106 of the strut 102 is subjected to capillary forces such that the wall faces 106 of the abutting struts 102 are curved toward each other to contact each other. The line bending is due to the contact of the wall surface 106 of the adjacent strut 102, which will eventually cause the opening 104 to close. Viscosity, for example, occurs at least at the point of interaction between adjacent pillars 108. Generally, line bending, particularly line sticking, is not desirable because it prevents, for example, access to the opening 104 during subsequent substrate processing steps, such as further deposition steps.

The capillary force also causes the structural material to bend and cause improper adhesion, which may damage the semiconductor substrate. The above disadvantages are particularly noticeable when depositing a substrate for a substrate having a high aspect ratio semiconductor pillar. The line curvature is caused by capillary pressure throughout the gas-liquid interface above the liquid trapped in the groove or through hole, causing the side walls to bend toward each other, and the side walls form high aspect ratio grooves or through holes. The high aspect ratio of the strut and the elastic constant of the strut itself also cause the line to bend. Due to the capillary pressure, this is sometimes referred to as capillary force, and the characteristic structure with narrow line width and high aspect ratio is susceptible to the difference in surface tension between the gas-liquid and liquid wall interfaces.

During the deposition, the more viscous flow film is unevenly distributed into the inter-pillar openings 104, and further line bending is caused by the lack of fluidity of the deposited film between the pillars. The initial surface roughness of the film deposited between the pillars also causes a non-uniform deposition distribution. The uneven surface reaction of the film deposited between the pillars with the native oxide also causes the lines to bend. Due to the rapid progress of device scaling, semiconductor processing is facing serious challenges in preventing line bending.

Therefore, an FCVD process is required in this field to reduce or eliminate line bending and local stress caused by deposition roughness.

In an embodiment of a 300 millimeter (mm) substrate, the method of reducing the line curvature and the surface roughness of the substrate with the struts includes at about 50 The substrate containing the pillars is treated with a radical to form a treated surface at a temperature of from about °C to about 800 °C, at a pressure of from about 10 mTorr to about 20 Torr. The free radical may be a silicon-based, a nitrogen-based or an oxygen-based, and the free radical may be introduced at a flow rate of from about 0.1 sccm (standard cubic centimeters per minute) to about 10,000 sccm. Processing area. The method comprises reacting an organic rhodium precursor and an oxygen precursor at a temperature of about 100 ° C or below, at a pressure of from about 0.5 Torr to about 10 Torr to form a dielectric film over the treated surface. The organic ruthenium precursor can be introduced into the treatment zone at a flow rate of from about 10 sccm to about 1800 sccm, and the oxygen precursor can be introduced into the treatment zone at a flow rate of from about 10 mgm (mg per minute) to about 1500 mgm. The method includes curing the dielectric film at a temperature of about 150 ° C or below.

In one embodiment, the method of reducing surface roughness and line bending of a substrate having a pillar comprises: causing an organic germanium precursor, an oxygen precursor at a temperature of about 100 ° C or less, at a pressure of about 0.5 Torr to about 10 Torr. The substance reacts with the radical precursor to form a dielectric film on the substrate containing the pillars. The organic germanium precursor can be introduced into the treatment zone at a flow rate of from about 10 sccm to about 1800 sccm. The oxygen precursor can be introduced into the treatment zone at a flow rate of from about 10 mgm to about 1500 mgm. The free radical precursor can be introduced into the free radical source at a flow rate of from about 600 sccm to about 1250 sccm. The method includes curing the dielectric film at a temperature of about 150 ° C or below. The free radical precursor may be selected from the group consisting of a nitrogen radical precursor, an oxy radical precursor, and a sulfhydryl radical precursor.

100‧‧‧Semiconductor device

102‧‧‧ pillar

104‧‧‧ openings

106‧‧‧ wall

108‧‧‧ interaction points

200‧‧‧ equipment

202‧‧‧Processing chamber

204‧‧‧Free radical source

206‧‧‧ gas inlet

208‧‧‧ catheter

210‧‧‧ free radical cavity

212‧‧‧Cover components

214‧‧‧ top board

216‧‧‧ Cover

218‧‧‧Sprinkler

219, 221‧‧‧ source/free radical source

220‧‧‧Support members

222‧‧‧ lining

223‧‧‧Distribution board

224‧‧‧ holes

226‧‧‧ openings

228‧‧‧Processing area

230‧‧‧ Subject

232‧‧‧Support components

234‧‧‧ lining

235‧‧‧Square valve (opening)

236‧‧‧ mouth

238‧‧‧ pumping channel

240‧‧‧vacuum system

242‧‧‧vacuum

244‧‧‧ valve

246‧‧‧Vacuum pump

248, 250‧‧‧ surface

252‧‧‧Support members

254‧‧‧ Lifting mechanism

256‧‧‧ shaft

258‧‧‧ openings

260‧‧‧ telescopic tube

262‧‧‧ heating element

264‧‧‧cooling channel

302, 304‧‧‧ surface

306‧‧‧ internal volume

308, 310, 316‧‧ channels

312, 314‧‧ Entrance

402, 404, 406, 408, 410‧‧‧ blocks

In order to make the above summary of the present invention more obvious and understood, the description may be made in conjunction with the reference embodiments. It is to be understood that the appended claims are not intended to

Fig. 1 is a view showing the effect of bending of the lines between the pillars due to the capillary force, and the pillars are formed in the structure of the semiconductor device on the substrate.

Figure 2 is a cross-sectional view of a device in accordance with an embodiment.

Figure 3 is a cross-sectional view of a two-channel showerhead that can be used with the apparatus of Figure 2.

4A through 4B are process flow diagrams, each of which illustrates a method in accordance with another embodiment.

To facilitate understanding, the same component symbols are used to represent common similar components in the various figures. It will be understood that the elements described in one embodiment may be beneficially utilized in other embodiments and are not described in detail herein. The illustrations are not to be construed as being drawn to scale unless otherwise specified. Also, the drawings are generally simplified and the details or components are omitted for clarity of illustration and description. The drawings and the description are used to illustrate the following principles, in which like reference

The present application claims the benefit of U.S. Provisional Patent Application No. 62/095,518, filed on Jan. 22, 2014, which is hereby incorporated by reference.

The description below refers to numerous specific details in order to provide a more thorough understanding of the embodiments. However, those skilled in the art will be clear The invention may be practiced without these specific details. In other instances, specific device structures are not described in order to avoid obscuring the described embodiments. The following description and drawings are merely illustrative of the embodiments and should not be construed as limiting.

The pillar-containing substrate may have a plurality of spaces as a spacer and a structure formed on the substrate. The space can have height and width to define the aspect ratio of height to width (ie, H/W), and the aspect ratio is significantly greater than 1:1 (eg, 5:1 or to 25:1 or more).

2 is a cross-sectional view of apparatus 200 for a germanium alkyl and/or free radical surface treatment of a dielectric film/substrate, in accordance with an embodiment of the present invention. As shown in FIG. 2, apparatus 200 includes a processing chamber 202 that includes a body 230 and a source of free radicals 204 coupled to body 230. The free radical source 204 can be any suitable source capable of generating free radicals. The free radical source 204 can be a remote plasma source such as a radio frequency (RF) or ultra high radio frequency (VHRF) capacitively coupled plasma (CCP) source, an inductively coupled plasma (ICP) source, a microwave induced (MW) plasma source. , DC glow discharge power supply, electron cyclotron resonance (ECR) chamber or high density plasma (HDP) chamber. Alternatively, the source of free radicals 204 can be the ultraviolet (UV) source or the filament of a hot wire chemical vapor deposition (HW-CVD) chamber. The free radical source 204 can include one or more gas inlets 206 that can be coupled to the processing chamber 202 by a free radical conduit 208.

One or more process gases may enter the radical source 204 via one or more gas inlets 206, which may be free radical forming gases and may be a gas mixture. The one or more process gases may comprise oxygen and/or nitrogen containing gases such as oxygen, H ₂ O (water), hydrogen peroxide, and/or ammonia. Alternatively or in addition to oxygen and/or nitrogen containing, the process gas may comprise a helium containing gas. Examples of the ruthenium containing gas include organic ruthenium, tetraalkyl orthosilicate gas, and dioxane. The organic germanium gas includes an organic compound gas having at least one carbon-hydrazine bond. The tetraalkyl orthosilicate gas includes a gas composed of four alkyl groups attached to the SiO _{4 4} ^- ion. More particularly, one or more of the precursor gases may be (dimethylhydrazino)(trimethyldecyl)methane ((Me) ₃ SiCH ₂ SiH(Me) ₂ ), hexamethyldioxane ((Me) ₃ SiSi(Me) ₃ ), trimethyldecane ((Me) ₃ SiH), trimethyldecane chloride ((Me) ₃ SiCl), tetramethylnonane ((Me) ₄ Si), tetraethoxy矽 ((EtO) ₄ Si), tetramethoxy decane ((MeO) ₄ Si), 肆 (trimethyl decyl) decane ((Me ₃ Si) ₄ Si), (dimethylamino) dimethyl Base decane ((Me ₂ N)SiHMe ₂ ), dimethyldiethoxy decane ((EtO) ₂ Si(Me) ₂ ), dimethyldimethoxydecane ((MeO) ₂ Si(Me) ₂ ), methyltrimethoxydecane ((MeO) ₃ Si(Me)), dimethoxytetramethyldioxane (((Me) ₂ Si(OMe)) ₂ O), tris (dimethyl) Amino) decane ((Me ₂ N) ₃ SiH), bis(dimethylamino)methyl decane ((Me ₂ N) ₂ CH ₃ SiH), dioxane ((SiH ₃ ) ₂ O) and The above composition.

The helium containing gas can react with the surface of the substrate, such as with Si-OH, to form a ruthenium functionalized substrate surface. Alternatively or additionally, the helium containing gas can form a conformal layer on the substrate. As compared to untreated surfaces The Si-OH dangling bonds, ruthenium functionalization and/or ruthenium deposition on the substrate surface reduce the intermolecular forces between adjacent pillars, such as hydrogen bonds. The nitrogen-containing gas and the oxygen-containing gas have similar effects on the surface of the untreated substrate.

The one or more process gases may comprise an inert gas, such as argon. Free radicals (eg, oxygen, nitrogen, or helium radicals) generated by the free radical source 204 enter the processing chamber 202 via the free radical conduit 208. The processing conditions can be optimized to achieve a predetermined uniformity of the surface content of the nitrogen, oxygen and/or ruthenium substrate.

The free radical conduit 208 is a component of the lid assembly 212, which also includes a free radical chamber 210, a top plate 214, a lid rim 216, and a dual channel showerhead 218. The free radical conduit 208 can comprise a material that does not substantially react with free radicals. For example, the radical conduit 208 may comprise AlN, SiO ₂ , Y ₂ O ₃ , MgO, anodized Al ₂ O ₃ , sapphire, one or more Al ₂ O ₃ , sapphire, AlN, Y ₂ O ₃ , MgO Ceramic or plastic. A representative example of a suitable SiO ₂ material is quartz. Alternatively or in addition, the surface of the free radical conduit 208 that contacts the free radicals during operation may have a coating. The coating may also comprise AlN, SiO ₂ , Y ₂ O ₃ , MgO, anodized Al ₂ O ₃ , sapphire, ceramic or plastic containing one or more Al ₂ O ₃ , sapphire, AlN, Y ₂ O ₃ , MgO. . If a coating is used, the coating thickness can range from about 1 micrometer (μm) to about 1 mm. The coating can be applied using a spray coating process. The free radical conduit 208 can be disposed within or supported by the free radical conduit support member 220. The free radical conduit support member 220 can be disposed on the top plate 214 with the top plate disposed on the cover rim 216.

The radical cavity 210 is disposed below and coupled to the free radical conduit 208, and free radicals generated by the radical source 204 enter the radical cavity 210 via the free radical conduit 208. Directional terms as used herein, such as "below", "above", "below", "top" or "bottom", are relative to the base plane of the chamber, not the absolute direction. The free radical chamber 210 is defined by a top plate 214 that is coupled to the cover rim 216, and the cover edge is coupled to the dual channel showerhead 218. The radical cavity 210 can include a liner 222, as appropriate. Liner 222 may cover the surface of top plate 214 and cover rim 216 within free radical cavity 210. Liner 222 can comprise a material that does not substantially react with free radicals. For example, the liner 222 may comprise AlN, SiO ₂ , Y ₂ O ₃ , MgO, anodized Al ₂ O ₃ , sapphire, ceramics containing one or more Al ₂ O ₃ , sapphire, AlN, Y ₂ O ₃ , MgO. Or plastic. Alternatively or in addition, the surface of the free radical cavity 210 that contacts the free radical may be composed of or coated with a material that does not substantially react with the free radical. For example, the surface may be composed of AlN, SiO ₂ , Y ₂ O ₃ , MgO, anodized Al ₂ O ₃ , sapphire, ceramic or plastic containing one or more Al ₂ O ₃ , sapphire, AlN, Y ₂ O ₃ , MgO. Or apply the material. If a coating is used, the coating thickness can range from about 1 [mu]m to about 1 mm. The free radical flux to the substrate placed in the processing chamber 202 will increase by not consuming free radicals.

Typically, an activation gas system produced by excitation of energy such as gaseous molecules consists of a plasma of charged ions, free radicals, and electrons. In some processes where plasma free radicals are desired (reactive to the ruthenium or polycrystalline ruthenium material on the substrate by plasma radicals in comparison to ions or radicals and ionic mixtures), the free radical distribution plate 223 can be used as an ion. A filter, such as an electrostatic filter, a filament or mesh filter, or a magnetic filter, is used between the top plate 214 and the dual channel showerhead 218 to eliminate all or substantially all of the plasma The ions cause only plasma radicals to flow through the dual channel showerhead 218 and react with the tantalum or polysilicon material on the substrate to provide greater selectivity to the substrate surface treatment. In the case where the radicals of the radical source 204 flow through the dual channel showerhead 218, the dual channel showerhead 218 can be turned on with a small amount of power to promote free radical regeneration to compensate for free radical losses due to the flow path, or to utilize different RF frequency and other parameters to change the free radical composition. Alternatively, the electrodes of the dual channel showerhead 218 may not be powered. As such, plasma radicals from the free radical source 204 will bypass the dual channel showerhead 218 to avoid or reduce undesirable reactions in the processing zone 228.

The radical distribution plate 223 may be made of the same material as the liner 222 or may be coated with the same material as the liner 222. Free radical distribution plate 223 can be used to control the free radical flow profile. The position of the radical distribution plate 223 in the radical chamber 210 (i.e., the distance between the radical distribution plate 223 and the top plate 214 and the distance between the radical distribution plate 223 and the dual channel showerhead 218) can also be adjusted to affect free radicals. distributed.

The free radical distribution plate 223 includes a plurality of pores configured to control the activation gas (ie, ions, free radicals, and/or neutral species) through the free radical distribution plate 223. For example, the aspect ratio of the holes (ie, the diameter of the holes versus the length) and/or the geometry of the holes can be controlled to reduce the passage of ionically charged species in the activating gas through the free radical distribution plate 223. The holes of the radical distribution plate 223 include, for example, a cylindrical portion facing the top plate 214 and a tapered portion facing the two-channel shower head 218. The cylindrical portion can be shaped and sized to control the flow of ionic species to the dual channel showerhead 218. An adjustable electrical bias can also be applied to the free radical distribution plate 223 as an additional means to control the ionic species The species flows through the free radical distribution plate 223. Controlling the ionic species through the amount of free radical distribution plate 223 enhances the control of the activating gas to contact the underlying substrate, thereby enhancing the surface treatment characteristics of the control gas mixture. For example, adjusting the ion concentration of the gas mixture can transfer the conformal to flow balance of the deposited dielectric material.

The free radicals then enter the processing zone 228 through a plurality of holes 224 provided in the dual channel showerhead 218. The dual channel showerhead 218 further includes a plurality of openings 226 having a diameter less than the plurality of holes 224.

A plurality of openings 226 are connected to an internal volume (not shown) that is not in fluid communication with a plurality of holes 224. At least two gas/free radical sources 219, 221 are coupled to the dual channel showerhead 218. The dual channel showerhead 218 can be heated or cooled. In one embodiment, the dual channel showerhead 218 is heated to between about 100 ° C and about 600 ° C. In another embodiment, the dual channel showerhead 218 is cooled to between about 25 ° C and about 75 ° C. One or more heating elements (not shown) and/or cooling elements (not shown) may be embedded in the dual channel showerhead 218. The heating element and the cooling element can be used to control the temperature of the dual channel showerhead 218 during operation. The heating element can be any suitable heating element, such as one or more resistive heating elements. The heating element can be connected to one or more power sources (not shown). Coolant can flow through the passage to cool the dual channel showerhead 218. The dual channel showerhead 218 will be described in detail later (Fig. 3).

Processing chamber 202 includes a lid assembly 212, a body 230, and a support assembly 232. The support assembly 232 is at least partially disposed within the body 230. The body 230 includes a narrow valve opening 235 for access to the processing chamber 202 internal. The body 230 includes a liner 234 that covers the inner face of the body 230. The liner 234 includes one or more apertures 236 formed therein and a pumping passage 238 that is in fluid communication with the vacuum system 240. The orifice 236 provides a path for gas to flow into the pumping passage 238, which provides gas discharge within the processing chamber 202. Alternatively, a port and pumping channel may be provided at the bottom of the body 230 from which gas may be withdrawn from the bottom of the body 230. Directional terms as used herein, such as "below", "above", "below", "top" or "bottom", are relative to the base plane of the chamber, not the absolute direction.

Vacuum system 240 includes a vacuum port 242, a valve 244, and a vacuum pump 246. Vacuum pump 246 is in fluid communication with pumping passage 238 via vacuum port 242. The aperture 236 allows the pumping channel 238 to be in fluid communication with the processing zone 228 within the body 230. Treatment zone 228 is defined by lower surface 248 of dual channel showerhead 218 and upper surface 250 of support assembly 232. Liner 234 surrounds processing zone 228. Directional terms as used herein, such as "below", "above", "below", "top" or "bottom", are relative to the base plane of the chamber, not the absolute direction.

The support assembly 232 includes a support member 252 for supporting a substrate (not shown) for processing within the body 230. The substrate can be of any standard size, such as 300 mm. Alternatively, the substrate can be greater than 300 mm, such as 450 mm or greater. The support member 252 may comprise AlN or aluminum depending on the operating temperature. The support member 252 can be configured to grip the substrate, and the support member 252 can be an electrostatic chuck or a vacuum chuck.

The support member 252 can be coupled to the lift mechanism 254 via a shaft 256 that passes through a centering opening 258 formed in a bottom surface of the body 230. The lifting mechanism 254 can be elastically sealed to the body 230 by the telescoping tube 260 to prevent vacuum leakage around the shaft 256. The lift mechanism 254 allows the support member 252 to move vertically between the processing position within the body 230 and the lower transfer position. The transfer position is slightly lower than the narrow valve opening 235. During operation, the spacing of the substrate from the dual channel showerhead 218 can be minimized to maximize the free radical flux on the substrate surface. For example, the spacing can be from about 100 mm to about 5000 mm. The lift mechanism 254 can be configured to rotate the shaft 256 with a rotor (not shown) coupled to the support member 252, thereby rotating the support member 252, causing the substrate placed on the support member 252 to rotate during operation. Substrate rotation helps to improve surface treatment uniformity.

One or more heating elements 262 and cooling passages 264 may be embedded in the support member 252. Heating element 262 and cooling passage 264 can be used to control the substrate temperature during operation. Heating element 262 can be any suitable heating element, such as one or more resistive heating elements. Heating element 262 can be coupled to one or more power sources (not shown). Heating elements 262 can be individually controlled to control multiple zones of heating or cooling with individual heating and/or cooling. Individually controlled multi-zone heating and cooling capabilities to enhance substrate temperature profile under different processing conditions. Coolant can flow through the passage 264 to cool the substrate. The support member 252 can further include a gas passage through the upper surface 250 to allow cooling gas to flow to the back side of the substrate.

The chamber 202 contains an RF source. The RF source can be coupled to the dual channel showerhead 218 or support member 252. RF source can be low frequency, high frequency or super high frequency. In one embodiment, as shown in FIG. 2, the dual channel showerhead 218 is coupled to the RF source and the support member 252 is coupled to ground. In another embodiment, the dual channel showerhead 218 is grounded and the support member 252 is coupled to the RF source. In either embodiment, capacitive coupling plasma may be formed in the processing region 228 between the dual channel showerhead 218 and the support member 252 during operation. When the source of free radicals is a remote source of plasma, a capacitively coupled plasma can be formed in the processing zone 228 in addition to forming a plasma from the source of free radicals. Support member 252 can utilize a DC source bias to increase activation gas bombardment. Therefore, the processing chamber 202 can be a PECVD/FCVD chamber, and the apparatus 200 can perform a cyclic process (alternating free radical application PECVD/FCVD).

Alternatively or in addition to the free radicals supplied by the free radical source 204, one or more nitrogen, oxygen and helium containing gases may be supplied to the substrate by a dual channel showerhead 218 for surface treatment. Figure 3 is a cross-sectional view of a dual channel showerhead 218 in accordance with the described embodiment. The dual channel showerhead 218 has a first surface 302 facing the radical cavity 210 and a second surface 304 opposite the first surface 302. The second surface 304 faces the support assembly 232. The first surface 302 is spaced apart from the second surface 304 to provide an interior volume 306. The first and second surfaces 302, 304 may be composed of or coated with a material that is substantially non-reactive with free radicals. For example, the surfaces 302, 304 may be AlN, SiO ₂ , Y ₂ O ₃ , MgO, anodized Al ₂ O ₃ , sapphire, ceramics containing one or more Al ₂ O ₃ , sapphire, AlN, Y ₂ O ₃ , MgO. Or plastic to make or coat the material. If a coating is used, the coating thickness can range from about 1 [mu]m to about 1 mm. A plurality of holes 224 are formed in the dual channel showerhead 218. The holes 224 may extend from the first surface 302 to the second surface 304, and free radicals generated by the radical source 204 may abut the substrate on the support assembly 232 through the holes 224. The inner volume 306 surrounds a plurality of holes 224, and the one or more annular channels 308, 310 surround the inner volume 306 and the plurality of holes 224.

Internal volume 306 is in fluid communication with one or more annular passages 308, 310. A plurality of openings 226 extend from the interior volume 306 to the second surface 304. One or more annular passages 308, 310 are coupled to the inlet 312 and the inlet is coupled to the gas source 221. The gas source 221 can provide a precursor gas to the dual channel showerhead 218, such as a helium containing gas, an oxygen containing gas, and/or a nitrogen containing gas, the precursor gas flowing through the one or more annular passages 308, 310 to the interior volume 306, And through a plurality of openings 226 to the processing zone 228.

Since the openings of the plurality of holes 224 are not in fluid communication with the interior volume 306, free radicals passing through the plurality of holes 224 are not mixed with the precursor gases in the dual channel showerhead 218. The showerhead 218 is a dual channel showerhead 218 because the showerhead 218 contains one or more channels that are not in fluid communication with one another. The showerhead 218 can contain more than two channels, also referred to as dual channel showerheads. Each of the plurality of holes 224 has an inner diameter of from about 0.10 Torr to about 0.35 Torr. The plurality of openings 226 each have a diameter of from about 0.01 吋 to about 0.04 吋.

One or more of the annular passages 308, 310 may be connected by one or more connecting passages 316 having a smaller cross section than the annular passages 308, 310. This configuration helps to distribute the precursor gas evenly to the interior volume 306 and away from the opening 226. However, if free radicals will enter the inlet 312, when flowing from the large annular passage 308 to the small connecting passage 316, Free radicals can be compounded. To provide a free radical path different from the free radicals formed in the free radical source 204, a second inlet 314 is formed in the dual channel showerhead 218, and the second inlet 314 is coupled to the interior volume 306 and bypasses one or more annular channels 308, 310. The second inlet 314 is different than the first inlet 312 and is configurable to direct free radicals from the radical source 219 to the interior volume 306 without passing through one or more of the annular passages 308, 310.

The processing conditions during the surface treatment using the apparatus 200 are as follows. The temperature of the processing chamber 202 can be maintained between about 50 ° C and 800 ° C, such as between about 100 ° C and about 600 ° C. The pressure of the processing chamber 202 can be maintained from about 10 mTorr to about 20 Torr, such as from about 0.5 Torr to about 8 Torr. For a 300 mm substrate, at least one cerium-, nitrogen-containing, and/or oxygen-containing precursor gas can be introduced into the processing zone 228 at a flow rate of from about 0.1 sccm to about 10,000 sccm. Alternatively or additionally, in the case of a 300 mm substrate, the radical forming gases may be introduced into the radical source 204 at a flow rate of from about 1 sccm to about 50,000 sccm. If used, the carrier gas flow rate can range from about 1 sccm to about 50,000 sccm for a 300 mm substrate. Alternatively or in addition to the dual channel showerhead 218, free radicals may be generated by the free radical source 204. For example, if the free radical source 204 is capacitively coupled to a remote plasma source, free radicals can be generated from about 50 watts (W) to about 15,000 W for a 300 mm substrate, such as an RF power of from about 2000 W to about 10000 W.

After the surface treatment, the more uniform the pillars on the surface of the treated substrate, the more the viscous force and the surface roughness between the pillars are reduced, compared to the pillars before the treatment and the surface of the entire substrate. Line bending and surface roughness available Microscope monitoring, such as scanning electron microscopy and tunneling electron microscopy. Other microscope techniques can also be used to monitor line bending. Using this technique, line bending can be monitored by calculating the standard deviation of the spacing of adjacent islands and/or recesses. For example, the average and standard deviation of twenty grains throughout the substrate can be calculated. A low standard deviation means that the line bends less than the substrate grain with a high standard deviation. Here, the uniformity refers to the inter-island spacing and/or the standard deviation of the space between the pillars. If the island/concave uniformity across the surface of the substrate is high, there will be less line bending.

According to an embodiment of the invention, the surface treatment can adjust the FCVD fill half moon profile and reduce the capillary forces between adjacent struts after a subsequent FCVD process. Reducing the surface reactivity of the substrate surface reduces the viscous force between the adjacent pillars of the substrate, and allows the subsequent FCVD process to fill the gap between adjacent pillars and reduce the bending of the lines before and during the FCVD process. Therefore, the surface treatment according to an embodiment of the present invention can adjust the initial deposition roughness of the treatment layer and the subsequent FCVD layer deposited onto the treatment layer.

Alternatively or in addition to the surface treatment described above, the fluidized layer can be formed on the treated or untreated substrate by a flow or flow-like CVD process. The fluidized layer is usually formed in a blanket manner, filling a recess of the patterned substrate and a convex portion covering the patterned substrate. The fluid layer can be an oxide layer.

The deposited dielectric film is generally more fluid at low plasma power and is transferred from fluidity to conformal as the power of the plasma increases. For example, when the plasma power is reduced from about 1000 watts to about 100 watts or less (e.g., about 900, 800, 700, 600, or 500 watts or less), the argon-containing plasma held in the processing zone 228 can be made more Fluidized yttria layer, when A more conformal layer will be produced when the plasma power is increased from about 1000 watts or more (e.g., about 1000, 1100, 1200, 1300, 1400, 1500, 1600, 1700 watts or more). As the plasma power is increased from low to high, it can be smoothed and continuously converted from fluidity to a conformal deposited film, or with a less continuous threshold. The plasma power (alone or in addition to other deposition parameters) can be adjusted to select the conformal and fluidity balance of the deposited film.

An exemplary process for forming an oxide layer over a patterned substrate includes reacting an organic germanium precursor with an oxygen precursor at a temperature of about 100 ° C or below to form a flowing oxide layer. Suitable organic germanium precursors have a carbon atom to germanium atom ratio of less than 8. Suitable organic germanium compounds also have an oxygen to germanium atomic ratio of from 0 to about 6, and include Si-O-Si crosslinks to aid in the formation of SiO _x films and to reduce carbon and hydroxyl contamination.

Suitable organic hydrazine compounds may be oxoxane compounds (e.g., triethoxy methoxy oxane, tetramethoxy methoxy oxane, trimethoxy methoxy oxane, hexamethoxydioxane, octamethoxy triterpene). Oxane and/or octamethoxydodecyloxane, a nonazepine having one or more nitrogen groups (for example, hexamethoxydiazepine, methylhexamethoxydioxane, Chlorhexamethoxydiazide, hexaethoxydiazide, pentylmethoxytrioxane and octamethoxycycloxetane, including one or more halogen moieties ( Halogenated oxane compounds such as fluoride, chloride, bromide or iodide (eg tetrachloromethane, dichlorodiethoxy decane, chlorotriethoxy decane, hexachlorodioxane) And/or octachlorotrioxane and amino decane (eg trioxane, hexamethyldioxane, azaindene tricyclic, decyl (dimethylamino) decane, bis(diethylamine) Base) decane, tris(dimethylamino)chlorodecane and methyl azaindene tricyclic). Suitable organic hydrazine compounds may also be dioxane, such as alkoxydioxane, alkoxyalkyldioxane and alkoxyethoxycarbonyldioxane, including compounds having the general structure: Wherein R _{1 to} R _{6 are each} independently a C _1-3 alkoxy group, a C _1-3 alkyl group or an ethoxylated group, wherein at least one of R _{1 to} R ₆ is an alkoxy group or an ethoxy group. Suitable organic phosphonium compounds also include cyclic dioxanes having alkyl and alkoxy moieties such as butane, pentanane, hexancan, heptane, octane, and the like having at least one alkyl group and alkoxy group. Examples include octamethyl-1,4-dioxa-2,3,5,6-tetraoxacyclohexane, 1,4-dioxa-2,3,5,6-tetradecylcyclohexane Other alkoxyalkylcyclodecanes such as 1,2,3,4,5,6-hexamethoxy-1,2,3,4,5,6-hexamethylcyclohexane. Suitable organic hydrazine compounds also include organic cyclodecanes such as cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane and the like.

The oxygen precursor may include molecular oxygen (O ₂ ), ozone (O ₃ ), nitrogen oxides (eg, NO, NO ₂ or N ₂ O), hydroxides (eg, water or hydrogen peroxide), carbon oxides (eg, Carbon monoxide or carbon dioxide) and other oxygenated precursors. The oxygen precursor may also include atomic oxygen and/or oxygen radicals, which may be generated remotely and with the introduction of an organic rhodium precursor. A carrier gas such as helium, neon, argon, and/or hydrogen may be mixed with the organic cerium precursor, the oxygen precursor, or both. The oxygen precursor can be activated prior to introduction into the deposition chamber, such as with a remote plasma source, including thermal dissociation, ultraviolet light dissociation, radio frequency (RF), direct current (DC), and/or microwave dissociation. In one embodiment, 4-6 kilowatts (kW) of RF power is coupled to 900-1800 sccm of argon and 600-1200 sccm of molecular oxygen flow. The heating temperature may range from room temperature to about 1100 °C.

The organic ruthenium precursor and the oxygen precursor are typically introduced into the deposition chamber by different paths to avoid reaction outside the deposition chamber. The organic germanium precursor can be introduced into the deposition chamber at a liquid equivalent flow rate of from about 800 mgm to about 1600 mgm like a gas. The crucible may be incorporated as a carrier gas at a flow rate of from about 600 sccm to about 2400 sccm. The activated oxygen precursor can be introduced into the deposition chamber at a flow rate of from about 3 sLm (standard liters per minute) to about 20 sLm. The precursor reacts to deposit a flowing oxide layer onto the substrate with the patterned photoresist material. The flowing oxide flows to fill the recess of the patterned substrate. In one embodiment, the flowing oxide layer may be yttrium oxide and deposited to a thickness of 200-400 angstroms ( And covering the material protrusions.

The organic rhodium precursor can be used to form a fluidized layer at a processing temperature of from about -10 ° C to about 150 ° C (eg, from about 30 ° C to about 100 ° C, such as about 65 ° C) and a pressure of from about 0.5 Torr to about 10 Torr. The organic germanium precursor can be provided at a flow rate of from about 10 sccm to about 1800 sccm, such as from about 600 sccm to about 1600 sccm, such as about 1400 sccm. The oxygen precursor can be provided at a flow rate of from about 10 mgm to about 1500 mgm, for example about 1000 mgm.

The nitrogen radical precursor may also be provided to a source of free radicals, for example about 800 sccm, at a flow rate of from about 600 sccm to about 1250 sccm. Introducing a nitrogen group into the treatment zone during formation of the flowing SiO layer 228 can reduce the viscous force of the substrate adjacent to the pillar during deposition, improve the capillary force and the surface roughness of the deposited SiO film. The higher flow rate values of the above-described cesium alkyl gas and radical gas range can improve the fluidity of the film, the line bending of the substrate, and the roughness and mechanical strength of the deposited FCVD film. In some embodiments, the ratio of organic ruthenium precursor flow to nitrogen radical flow rate is from about 1:1 to about 10:1, such as about 2:1. The nitrogen radical gas can be derived from, for example, ammonia.

As described above, when a flowing SiO film is deposited onto a substrate that has not been surface-treated, similar beneficial results can be obtained with a smaller nitrogen radical flow rate (e.g., 600 sccm).

Similar beneficial results are obtained when a thiol and oxy radical are substituted or a nitrogen radical is supplied to the treatment zone 228. The sulfhydryl and oxy radical sources can be derived from the above-described surface treatment sulfhydryl and oxy precursors. Like the conditions of the nitrogen radical free FCVD process, similar processing conditions can be used for the sulfhydryl and oxy radical FCVD processes. Similar beneficial results are obtained when other decane gases are used as a source for depositing a flow film (i.e., the flow dielectric film is not necessarily an SiO film).

The flowing film typically cures after deposition to remove moisture and residual organics, harden and densify the layer. Curing is typically carried out using a low temperature process to maintain the magnetically activated material at a temperature of about 100 ° C or below. Processes include contact inductively coupled plasma, ultraviolet light, ozone, electron beam, acidic or basic vapors, aqueous environments (eg, heated deionized water), and combined or sequential such treatments. To aid in curing, the surface oxide method can be used to heat the flowing oxide layer to about 150 ° C or below. Surface heating method This includes touching infrared or heat lamps and proximity to the surface of the thermal chamber, such as a showerhead. If the substrate is placed on a substrate support capable of cooling the magnetically active material, the flowing oxide layer can be heated to a higher temperature depending on the cooling capacity of the substrate support.

In other embodiments, the substrate is heated using a heat source that is applied to the surface of the substrate opposite the oxide layer to cure the oxide layer. For example, the substrate can be placed on a heated substrate support to cure the oxide layer, and the substrate support can be heated to heat the substrate from about 100 ° C to about 150 ° C.

The flow oxide layer used herein may be partially cured as desired to reduce the cure time or to achieve a predetermined property of the cured oxide layer. The normally flowing oxide layer cures to a certain extent sufficient to form a pattern and be maintained by the cured oxide layer without flowing. If the curing is based on the moisture after curing plus the organic matter in the residual layer divided by the percentage of the original moisture plus the organic matter, 0% means the uncured layer, such as the newly deposited flowing oxide layer, 100% means curing To the extent that all moisture and organic layers have been removed, the flow oxide layer used herein is typically cured to at least about 40%, such as from about 50% to about 95%, such as about 90%.

In some embodiments, the film may be formed onto the treated or untreated film surface using, for example, FCVD. The film may include a ruthenium-containing film, but is not limited thereto. For example, the film can be deposited and composed of SiC, SiO, SiCN, SiO ₂ , SiOC, SiOCN, SiON, and/or SiN. The film composition depends on the composition of the precursor gas. The SiC film can be deposited using, for example, (dimethylmethyl) (trimethylindenyl)methane, hexamethyldioxane, and/or trimethyldecane. The SiO/SiO ₂ film can be deposited using, for example, TEOS and/or dioxane. The SiCN film can be deposited using, for example, tris(dimethylamino)decane, bis(dimethylamino)methylnonane, and/or (dimethylamino)dimethyl decane. The SiOC film can utilize, for example, tris(dimethylamino)decane, bis(dimethylamino)methylnonane, (dimethylamino)dimethylsilane, tris(dimethylamino)decane, double (Dimethylamino)methyl decane and / or (dimethylamino) dimethyl decane deposition. The SiOCN film can be formed using, for example, tris(dimethylamino)decane, bis(dimethylamino)methylnonane, and/or (dimethylamino)dimethylsilane. The SiON film can be formed using, for example, dioxane or tridecylamine. The SiN film can be deposited using, for example, trioxane amine (TSA) and/or decane.

The flow or imitation flow layer can be formed using other systems such as high density plasma CVD systems, plasma enhanced CVD systems, and/or sub-atmospheric CVD systems. CVD system capable of forming an oxide layer to flow or simulated flow ETERNA CVD ^® Examples include the ULTIMA HDP CVD ^® systems and PRODUCER ^® system, both from Applied Materials of Santa Clara, California company (Applied Materials, Inc.). Other similarly constructed CVD systems from other manufacturers may also be used.

Figure 4A is a process flow diagram that illustrates a method in accordance with another embodiment. As shown in FIG. 4A, a method of reducing the curvature of a line and the surface roughness of a substrate having a strut includes treating the substrate containing the strut with a radical to form a treated surface (block 402). As described above, treating the substrate containing the pillars with free radicals to form the treated surface can be carried out at a temperature of from about 50 ° C to about 800 ° C, at a pressure of from about 10 mTorr to about 20 Torr. The free radical can be a thiol, a nitrogen or an oxy group, and the free radical can be introduced into the treatment zone at a flow rate of from about 0.1 sccm to about 10,000 sccm. Method includes making organic The ruthenium precursor reacts with the oxygen precursor to form a dielectric film over the treated surface (block 404). The reaction of the organic cerium precursor with the oxygen precursor to form a dielectric film over the treated surface can be carried out at a temperature of about 100 ° C or below, at a pressure of from about 0.5 Torr to about 10 Torr. The organic hafnium precursor can be introduced into the treatment zone at a flow rate of from about 10 sccm to about 1800 sccm, and the oxygen precursor can be introduced into the treatment zone at a flow rate of from about 10 mgm to about 1500 mgm. The method includes curing the dielectric film at a temperature of about 150 ° C or below (block 406). Embodiments of the present invention can improve substrate surface roughness and overall line bending of the substrate struts by improving capillary forces and viscous forces between adjacent struts.

Figure 4B is a process flow diagram that illustrates a method in accordance with yet another embodiment. As shown in FIG. 4B, the method for reducing the surface roughness of the substrate and the surface roughness of the substrate having the pillar includes reacting the organic germanium precursor, the oxygen precursor, and the radical precursor to form a dielectric film on the substrate including the pillar (square) 408). Forming the dielectric film over the substrate containing the pillars can be carried out at a temperature of about 100 ° C or below, at a pressure of from about 0.5 Torr to about 10 Torr. The organic germanium precursor can be introduced into the treatment zone at a flow rate of from about 10 sccm to about 1800 sccm. The oxygen precursor can be introduced into the treatment zone at a flow rate of from about 10 mgm to about 1500 mgm. The free radical precursor can be introduced into the free radical source at a flow rate of from about 600 sccm to about 1250 sccm. The method includes curing the dielectric film at a temperature of about 150 ° C or below (block 410). The free radical precursor may be selected from the group consisting of a nitrogen radical precursor, an oxy radical precursor, and a sulfhydryl radical precursor.

Embodiments of the present invention can improve capillary forces and viscous forces between adjacent struts, thereby improving substrate surface roughness and overall line bending of the substrate struts. Embodiments of the invention may also improve the fluidity of the deposited flow membrane.

While the above is directed to the embodiments of the present invention, the scope of the present invention is defined by the scope of the appended claims.

Claims (20)

A method for reducing surface roughness and line bending of a substrate having a pillar, comprising: forming a plurality of first radicals and ions in a distal plasma system, the remote plasma system being a radical source; Forming a plurality of second radicals in the showerhead; using at least the first radicals and the second at a temperature of from about 50 ° C to about 800 ° C, a pressure of from about 10 mTorr to about 20 Torr Free radical treatment of a substrate comprising pillars to form a treated surface, wherein the first radicals and the second radical are silicon-based, nitrogen-based or oxygen-based And the first radical and the second radical are introduced into a treatment zone at a first rate of from about 0.1 sccm to about 10,000 sccm; at a temperature of about 100 ° C or below, from about 0.5 Torr to about 10 Torr Reacting at least one of the first radicals and the second radical, an organic germanium precursor, and an oxygen precursor under pressure to form a dielectric film on the surface of the treatment, wherein the organic germanium precursor Introducing a treatment zone at a first rate of from about 10 sccm to about 1800 sccm, the oxygen precursor being about 10 mgm A first rate of about 1500 mgm is introduced into the treatment zone; and the dielectric film is cured at a temperature of about 150 ° C or below. The method of claim 1, wherein forming the dielectric film over the processing surface further comprises providing a radical precursor to the radical source at a first rate of from about 600 sccm to about 1250 sccm. The method of claim 1, wherein at least one of the first radical and the second radical is anoxy group and is derived from one or more selected from the group consisting of oxygen, H ₂ O, and hydrogen peroxide. Multiple compounds. The method of claim 1, wherein at least one of the first radical and the second radical is sulfhydryl, and is derived from a group selected from (dimethyl decyl) (trimethyl decyl) methane ( Me) ₃ SiCH ₂ SiH(Me) ₂ ), hexamethyldioxane ((Me) ₃ SiSi(Me) ₃ ), trimethyldecane ((Me) ₃ SiH), trimethyl decane chloride (Me ₃ SiCl), tetramethyl decane ((Me) ₄ Si), tetraethoxy decane ((EtO) ₄ Si), tetramethoxy decane ((MeO) ₄ Si), ruthenium (trimethyl fluorenyl) ) decane ((Me ₃ Si) ₄ Si), (dimethylamino) dimethyl decane ((Me ₂ N)SiHMe ₂ ), dimethyldiethoxy decane ((EtO) ₂ Si(Me) ₂ ), dimethyldimethoxydecane ((MeO) ₂ Si(Me) ₂ ), methyltrimethoxydecane ((MeO) ₃ Si(Me)), dimethoxytetramethyldioxane Alkane ((Me) ₂ Si(OMe)) ₂ O), tris(dimethylamino)decane ((Me ₂ N) ₃ SiH), bis(dimethylamino)methyldecane (Me ₂ One or more compounds of the group consisting of N) ₂ CH ₃ SiH) and dioxane ((SiH ₃ ) ₂ O). The method of claim 1 wherein forming the processing surface further comprises controlling an ion flux through the free radical distribution plate toward the substrate comprising the pillars. The method of claim 1 wherein the showerhead is a dual channel showerhead. A method for reducing surface roughness and line bending of a substrate having a pillar, comprising: forming a plurality of first radicals and ions in a distal plasma system, the remote plasma system being a radical source; Forming a plurality of second radicals in the showerhead; treating a substrate having pillars with the first radicals and the second radicals to form a treated surface; at a temperature of about 100 ° C or below, about An organic germanium precursor, an oxygen precursor, and at least one of the first radical and the second radical are reacted at a pressure of from 0.5 Torr to about 10 Torr to form a substrate on the pillar Forming a dielectric film, wherein the organic germanium precursor is introduced into a treatment zone at a first rate of about 10 sccm to about 1800 sccm, and the oxygen precursor is introduced into the treatment zone at a first rate of about 10 mgm to about 1500 mgm, a radical precursor is pressed Introduced at a rate of about 600 sccm to about 1250 sccm a source of free radicals; and curing the dielectric film at a temperature of about 150 ° C or below, wherein the radical precursor is selected from the group consisting of a nitrogen radical precursor, an oxy radical precursor, and a sulfhydryl radical precursor a group consisting of. The method of claim 7, wherein the organic ruthenium precursor is selected from the group consisting of triethoxy decane, tetramethoxy decane, trimethoxy decane, hexamethoxydioxane, and octadec. A group consisting of oxytrioxane and octamethoxydodecane. The method of claim 7, wherein the organic ruthenium precursor is selected from the group consisting of hexamethoxydiazide, methylhexamethoxydioxane, hexamethyloxydiazide, and hexaethylene. An azide alkane group consisting of oxydiazide azide, hexamethoxytrixaluminoxane and octamethoxycyclononanoxane. The method of claim 7, wherein the organic ruthenium precursor is selected from the group consisting of tetrachloromethane, dichlorodiethoxy decane, chlorotriethoxy siloxane, hexachlorodioxane, and octachlor A monohalogenated alkane of the group consisting of trioxane. The method of claim 7, wherein the organic ruthenium precursor is selected from the group consisting of tridecylamine, hexamethyldioxane, azaindene tricyclic, decyl (dimethylamino) decane, and bis (diethyl) Group consisting of decyl, decane, tris(dimethylamino)chlorodecane and methyl azaindene Monoamine decane. The method of claim 7, wherein the organic ruthenium precursor is selected from the group consisting of alkane, alkoxydioxane, and alkoxyethoxy dioxane. And consists of a compound having the following general structure, Wherein R _{1 to} R _{6 are each} independently a C _1-3 alkoxy group, a C _1-3 alkyl group or an ethoxylated group, wherein at least one of R _{1 to} R ₆ is a monoalkoxy group or an ethoxycarbonyl group. The method of claim 7, wherein the organic ruthenium precursor is selected from the group consisting of octamethyl-1,4-dioxa-2,3,5,6-tetraoxacyclohexane, 1,4-di Oxa-2,3,5,6-tetradecylcyclohexane, 1,2,3,4,5,6-hexamethoxy-1,2,3,4,5,6-hexamethylcyclohexane Monocyclic decane consisting of decane, cyclobutane, cyclopentane, cyclohexane, cycloheptane and cyclooctane. The method of claim 7, wherein the oxygen precursor is selected from the group consisting of oxygen, ozone, NO, NO ₂ , N ₂ O, water, peroxide, carbon monoxide, and carbon dioxide. The method of claim 7, wherein the organic cerium precursor, the oxygen precursor, and at least one of the first radical and the second radical are reacted at a temperature of about 65 °C. The method of claim 7, wherein the ratio of the organic ruthenium precursor flow rate to the at least one of the first radicals and the second radicals is between 1:1 and 10:1. The method of claim 7, wherein the radical precursor is a nitrogen radical precursor. The method of claim 7, wherein the radical precursor is a fluorenyl radical precursor and is selected from the group consisting of (dimethyl decyl) (trimethyl decyl) methane, hexamethyldioxane, three Methyl decane, trimethyl decane chloride, tetramethyl decane, tetraethoxy decane, tetramethoxy decane, decyl (trimethyl decyl) decane, (dimethylamino) dimethyl decane, Dimethyldiethoxydecane, dimethyldimethoxydecane, methyltrimethoxydecane, dimethoxytetramethyldioxane, tris(dimethylamino)decane, double (two A group consisting of methylamino)methylnonane and dioxane. The method of claim 7, wherein the radical precursor is a monooxy radical precursor and is selected from the group consisting of oxygen, H ₂ O, and hydrogen peroxide. The method of claim 7, wherein the radical precursor is ammonia.